Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE OF THE INVENTION
Condensation heat exchanger
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to a condensation heat exchanger
for condensation of nonmetallic vapors, and in
particular to a coating of the heat transfer surfaces
of the condensation heat exchanger. The coating is used
to extend the service life of the cooling tubes and to
improve the heat transfer at the heat transfer
surfaces.
Discussion of Background
In condensation heat exchangers, the lifespan of the
heat transfer surfaces plays an important role, since
damage to the heat transfer surfaces causes the entire
installation in which the condensation heat exchanger
is installed to fail. The state of the heat transfer
surfaces of condensation heat exchangers is adversely
affected, inter alia, by drop impingement erosion and
corrosion. Damage caused by drop impingement erosion
occurs in particular at those heat transfer surfaces
which are exposed to a high-speed flow of steam. There,
drops which are present in the steam which is to be
condensed impinge on the heat transfer surfaces, energy
being transferred to the surface by the impact or by
shear forces. Erosion occurs if, in the event of very
frequent drop impingement, the energy transferred is
sufficient to plastically deform the surface material,
leads to creep in the case of ductile materials or
leads to intercrystalline fatigue failure in the case
of hard materials.
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With steam condensers in steam power plants, it has
been observed that relatively large drops with
diameters in the region of 100 m and velocities of 250
m/s cause drop impingement erosion. In particular the
cooling tubes at the periphery of a tube bundle are
effected, while the tubes in the interior of a tube
bundle remain protected from direct drop impingement
erosion.
The occurrence of drop impingement erosion is highly
dependent on the materials properties, such as
hardness, ductility, elasticity, microstructure and
roughness, materials made from titanium and titanium
alloys being distinguished by a certain resistance to
erosion, although this resistance is insufficient and
predominantly due to their high hardness. In the case
of steam condensers used in steam power plants, drop
impingement erosion of this type is inhibited by a
suitable selection of material for the cooling tubes,
such as for example for stainless steel, titanium or
chromium.
Furthermore, drop impingement erosion presents a
problem in particular at low condenser pressures and
therefore relatively high vapor velocities, as for
example in steam condenses in steam power plants which
are operating at part loads. When steam condenses on
heat transfer surfaces, according to the prior art a
film of condensate which spreads over the entire
surface is formed. This film of condensate increases
the overall thermal resistance between steam and
cooling liquid flowing in the tubes, with the result
that the heat transfer capacity is reduced. For this
reason, there have long been efforts made to provide
heat transfer surfaces with a coating which, by dint of
hydrophobic properties, prevent the formation of a film
of condensate, so that drop condensation occurs at the
surface. The formation of drops allows the condensate
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hydrophobic properties, prevent the formation of a film of
condensate, so that drop condensation occurs at the
surface. The formation of drops allows the condensate to
run off more quickly than if a film is formed. As a
result, the surface of the heat exchanger is cleared, so
that vapor can condense again at the surface without being
impeded by a film of condensate. The overall heat
resistance therefore remains relatively low. By way of
example, layers of Teflon or enamel have been tried for
this purpose, but without great success, since these layers
had little resistance to erosion and corrosion.
In terms of the coating, it is important to solve the
problem of the resistance to erosion and corrosion and also
that of the bonding of the coating to the heat transfer
surfaces. These problems need to be solved in particular
in view of the desired long operating time of the
condensation heat exchanger, such as for example in the
cooling tubes of a steam condenser, which have to be able
to operate for a period of several years.
An example of a coating is disclosed by WO 96/41901 and EP
0 625 588. These documents describe a metallic heat
transfer surface with what is described as a hard-material
layer comprising plasma-modified amorphous hydrocarbon
layers, also known as diamond-like carbon. Amorphous
carbon is known for its elastic, extremely hard and
chemically stable properties. The wetting properties of
the hard-material layer of amorphous carbon are altered by
the incorporation of elements such as fluorine and silicon,
in such a manner that the layer acquires hydrophobic
properties. For bonding to the substrate, an interlayer is
applied between the substrate and the hard-material layer,
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the transition from the interlayer to the hard-material
layer being produced by means of a gradient layer.
However, the hard-material layer is ultimately only
resistant to erosion on account of its inherent hardness.
DE 34 37 898 has described a coating for the surfaces of a
heat exchanger, in particular for the surfaces of condenser
cooling tubes, comprising a triazine-dithiol derivative.
This layer material effects drop condensation and therefore
improves the heat transfer. Furthermore, the coating is
distinguished by good bonding to the cooling tubes.
DE 196 44 692 describes a coating comprising amorphous
carbon which brings about drop condensation on the cooling
tubes of steam condensers. The surface of a cooling tube
is roughened prior to the application of the amorphous
carbon, with the result that the effective interface
between the cooling tubes surface and the coating is
increased. As a result, the heat resistance between
coating and base material is reduced. After the coating,
the surface is smoothed, so that coated and uncoated
regions are formed next to one another.
SUMMARY OF THE INVENTION
Accordingly, one object of the invention is to provide a
novel coating for the heat transfer surfaces of a
condensation heat exchanger for the condensation of
nonmetallic vapors, the resistance of which with respect to
drop impingement erosion and corrosion is increased
compared to the prior art and at which, at the same time,
improved heat transfer is effected as a result of drop
condensation being brought about.
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According to the above object, from a broad aspect, the
present invention provides a condensation heat exchanger
having heat transfer surfaces for condensation of
nonmetallic vapours. The heat transfer surfaces have a
5 coating which contains amorphous carbon, and the surface of
the coating has hydrophobic properties. The coating, in
order to attenuate compression waves which originate from
the surface of the coating as a result of the impingement
of drops, has two or more layer pairs. A layer pair in
each case includes a hard layer comprising amorphous carbon
or a plasma polymer and a soft layer comprising amorphous
carbon or a plasma polymer. The hard and soft layers are
applied alternately and the last layer is a soft layer.
According to a further broad aspect of the present
invention there is provided a condensation heat exchanger
having heat exchanging surfaces for condensation of
nonmetallic vapour. The heat exchanging surfaces have a
coating which contains amorphous carbon. A surface of the
coating has hydrophobic properties. The condensation heat
exchanger is in the form of tube bundles comprising a
plurality of cooling tubes which are arranged vertically or
horizontally and on which vapor of any desired substance is
precipitated. The tube bundles have outer cooling tubes at
a periphery of the tube bundles and which outer cooling
tubes have a coating comprising two or more layer pairs. A
layer pair in each case includes a hard layer comprising
amorphous carbon or a plasma polymer and a soft layer
comprising amorphous carbon or a plasma polymer. The hard
and soft layers are applied alternately and the last layer
is a soft layer. The tube bundles have inner cooling tubes
which are provided with a coating comprising at least one
hard layer and at least one soft layer or a coating with
only a soft, hydrophobic layer comprising amorphous carbon.
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According to a still further broad aspect of the present
invention the heat transfer surfaces of a condensation heat
exchanger have a coating which contains amorphous carbon,
also known as diamond-like carbons. According to the
invention, the coating comprises a layer sequence including
at least one hard layer made from amorphous carbon and at
least one soft layer made from amorphous carbon, the hard
and soft layers being applied alternately and the bottom or
first layer on the heat transfer surface being a hard layer
and the top or last layer of the layer sequence being a
soft layer. The last, soft layer of the layer sequence in
particular has hydrophobic or water-repellent properties.
The coating according to the invention therefore, on
account of its last or outermost layer, makes the entire
layer system hydrophobic. This property is based on the
low surface energy of amorphous carbon when it is
relatively soft.
In the text which follows, the term amorphous carbon is to
be understood as meaning hydrogen-containing carbon layers
with a hydrogen content of 10 to 50 atomic o and with a
ratio of spa to sp2 bonds of between 0.1 and 0.9. In
general, it is possible to use all amorphous or dense
carbon layers produced by means of carbon or hydrocarbon
precursors as well as plasma polymer layers, polymer-like
or dense carbon and hydrocarbon layers, provided that they
have the hydrophobic properties and also the mechanical or
chemical properties of amorphous carbon mentioned below for
the production of layer sequences.
The wettability of the surface made from amorphous carbon
can be altered by varying its hardness. The higher the
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hardness, the greater the wettability becomes. A very hard
layer with a hardness of, for example, more than 3000
Vickers would be less suitable as an outermost, hydrophobic
layer than a layer of lower hardness.
The formation of extended films of condensate on the soft,
hydrophobic surface is prevented since the condensate
instead forms drops which, once they have reached a certain
size, run off the surface of the tube. In this case, on
the one hand a larger part of the area of the heat transfer
surface remains free of condensate, and on the other hand
the residence time of the condensate on a given heat
transfer surface is also greatly reduced. This increases
the heat transfer at the surfaces and ultimately improves
the performance of the condensation heat exchanger.
The layer sequence according to the invention, comprising
in each case a hard layer followed by a soft layer, in
particular effects an increased resistance to drop
impingement erosion. The impulse of impinging drops is
absorbed by the soft and hard layers by the compression
waves which originate in the surface material from the
impingement of the drops being attenuated by interference
by the pairs of hard and soft layers. This attenuation of
compression waves is similar to the attenuation of optical
waves brought about by layer pairs of thin layers with a
high and low refractive index, respectively.
The attenuation of compression waves is increased by a
layer sequence comprising a plurality of layer pairs of
hard and soft layers. A hardness in the range from 1500 to
3500 Vickers for the hard layers and hardness in the range
from 600 to 1500 Vickers for the soft layers is proposed.
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An optimum number of layers is dependent on the angle of
inclination of the direction of impingement of the drops on
the surface. If they impinge obliquely, a smaller number
of layers is required to attenuate the compression waves.
The overall heat resistance of the coated heat transfer
surface increases as the number of layers and the layer
thickness rise. Therefore, the number of layers is to be
optimized on the basis of the absorption of the compression
waves which originate from the impingement of drops and
also on the basis of the total heat resistance of the heat
transfer surfaces.
The combination of one or more layer pairs of hard and soft
layers produces a greatly improved resistance to erosion
compared to coatings comprising amorphous carbon with only
one layer of relatively high hardness. At the same time,
on account of its outermost, soft layer, the coating
according to the invention has the ability to form drop
condensation. As a result, increased resistance to drop
impact erosion and, at the same time, a high heat transfer
on account of the increased proportion of the area of the
heat transfer surface which is free of condensate are
ensured, so that both a lengthened service life of the heat
transfer surfaces and an increased capacity on the part of
the condensation heat exchanger are achieved.
The coating according to the invention is eminently
suitable for the cooling tubes of condensation heat
exchangers. The cooling tubes at which vapor of any
described material is precipitated are arranged vertically
or horizontally in tube bundles. In the case of a steam
condenser, such as for example in a steam power plant, in
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particular the cooling tubes at the periphery of a tube
bundle are more exposed to the drops which flow in at a
high velocity than cooling tubes in the interior of a
bundle. The two-layer or multi-layer coating is therefore
particularly suitable for those cooling tubes which lie at
the periphery. The cooling tubes in the interior of the
bundle can be provided with the same coating or merely with
a single, soft hydrophobic layer of amorphous carbon. This
effects drop condensation with the associated increase in
heat transfer. There is less need to protect against drop
impingement erosion there.
As has been mentioned, the drop condensation reduces the
residence time of the condensate on the cooling tubes of
the steam condenser. This results in a reduction in the
vapor-side pressure drop, the pressure drop being dependent
on the size of the tube bundle and the volume of the
condensate and on the tube clearance. The reduction in the
vapor-side pressure drop produces an improvement in the
overall heat transfer coefficient. Compared to condensers
with uncoated cooling tubes, it is possible to increase the
heat transfer coefficient by at least 250, with the
condensation heat exchanger being able to condense up to
20% more steam.
Furthermore, the coating is suitable for protecting against
erosion and corrosion in heat exchangers, such as for
example against ammonia erosion in steam condensers with
heat transfer surfaces made in copper alloys. A further
application is to protect against SO3 or NO2 corrosion in
condensers used in apparatus for recuperation of heat from
stack off-gases. In this application, the interfacial
energy must be very low compared to the surface tension of
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the condensate. Since the surface tension of sulphuric
acid is lower than that of water, therefore, the
interfacial energy of the outermost layer generally has to
be lower than in steam condensers. In this case, the
hardness of the outermost layer should be between 600 and
1500 Vickers.
Furthermore, the coating according to the invention can be
used in further condensation heat exchangers, such as for
example in refrigeration machines and indeed any heat
exchangers in which condensation takes place and drop
impingement erosion has to be prevented.
The coating according to the invention can be produced
using various, generally known production processes, such
as for example deposition by means of glow discharge in a
plasma comprising hydrocarbon-containing precursors, ion
beam coating and sputtering of carbon in hydrogen-
containing working gas. In these processes, the substrate
is exposed to a current of ions of several 100 eV. During
the glow discharge, the substrate is arranged in a reactor
chamber in contact with a cathode which is capacitively
connected to a 13.56 MHz RF generator. The grounded walls
of the plasma chamber form a larger counter electrode. In
this arrangement, it is possible to use any hydrocarbon
vapor or a hydrocarbon gas as first working gas for the
coating. To achieve particular layer properties, for
example different surface energies, hardnesses, optical
properties, etc., various gases are added to the first
working gas. By way of example, high or low surface
energies are achieved by adding nitrogen, fluorine- or
silicon-containing gases. The addition of nitrogen
additionally leads to an increase in the hardness of the
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layer which results. Furthermore, changing the bias
voltage across the electrodes between 100 and 1000 V makes
it possible to control the resulting hardness of the layer,
a high bias voltage leading to a hard, amorphous carbon
layer and a low voltage leading to a soft, amorphous carbon
layer.
In an exemplary embodiment, the hardness of a hard layer of
a layer pair is between 1500 and 3000 Vickers, while the
hardness of a soft layer of a layer pair is between 800 and
1500 Vickers. The thicknesses of the individual layers are
between 0.1 and 2 pm, preferably between 0.2 and 0.8 pm, if
a plurality of layers are applied in succession in the
layer sequence. The total layer thickness is in this case
in the range from 2 to 10 pm, preferably between 2 and 6
Jim. The thicknesses of the harder and softer layers are
preferably inversely proportional to their hardnesses.
The coating according to the invention includes at least
one layer pair comprising a hard layer and a soft layer.
In this case, a larger number of layer pairs can be
achieved, such as for example two layer pairs in each case
comprising one hard layer and one soft layer, provided that
the layer sequence begins with a hard layer and ends with a
soft layer with hydrophobic properties. The greater the
number of layers, the better the attenuation of the
impingement energy works, but also the higher the heat
resistance becomes, since the hard and soft layers have
different thermal conductivities, and the corresponding
heat resistances are cumulative.
The coating according to the invention bonds well to most
types of substrates, in particular with materials which
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form carbides, such as for example titanium, iron and
silicon as well as aluminum, but not to precious metals,
copper or copper-nickel alloys. In this case, it is not
necessary to roughen the substrate surface to improve the
bonding. If the coating is applied to a smooth substrate
surface, the result is a layer assembly which is even more
resistant to drop impingement erosion, since this reduces
the absorption of the impact energy by the base material.
Therefore, the coating according to the invention can be
applied to various substrate materials which are used for
the heat transfer surfaces, such as for example titanium,
stainless steel, chromium steels, aluminium and all
carbide-forming elements.
